Book/Report

FZJ-2017-03427

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Influence of electric field in the double layer on rate constants determined with electrochemical relaxation techniques for fast homogeneous proton transfer reactions in solution

Nürnberg, H. W. (Corresponding author)FZJ*

1965
Kernforschungsanlage Jülich, Verlag Jülich

Please use a persistent id in citations: http://hdl.handle.net/2128/14336

Report No.: Juel-0328-CA

Abstract: Electrochemical relaxation techniques, properly selected with respect to the time scale, offer a convenient way for the study of fast homogeneous chemical reactions in solution, provided a coupling to a suitable electrode process is possible. But inevitably the measured rate constants are influenced by the electric field in the double layer of the electrode. For the dissociation of uncharged acidsthe dissociation field effect may become dominant. The application of a correction, recently introduced by Barker on the basis of the electrical equivalent circuit for the faradaic impedance of the electrode, is outlined. The same correction may be obtained with the aid of the Gouy-Chapmantheory and Onsager's theory of the dissociation field effect, if a reasonable value for the distance of closest approach of the carboxylic group of the acid is presumed. Furthermore, the more complicated case of the complementary action of the static ift-effect and the dissociation field effect encountered in the study of charged acids is discussed. The conclusions, though drawn in terms of proton transfer reactions, apply generally to other types of fast chemical reactions.

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Contributing Institute(s):

1. Publikationen vor 2000 (PRE-2000)

Research Program(s):

1. 899 - ohne Topic (POF3-899) (POF3-899)

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Database coverage:

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